EP0002104A1 - Pleochroitische Farbstoffe geeignet zur Verwendung in Lösung mit flüssigen kristallinen Materialien für elektro-optische Einrichtungen - Google Patents

Pleochroitische Farbstoffe geeignet zur Verwendung in Lösung mit flüssigen kristallinen Materialien für elektro-optische Einrichtungen Download PDF

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EP0002104A1
EP0002104A1 EP78300487A EP78300487A EP0002104A1 EP 0002104 A1 EP0002104 A1 EP 0002104A1 EP 78300487 A EP78300487 A EP 78300487A EP 78300487 A EP78300487 A EP 78300487A EP 0002104 A1 EP0002104 A1 EP 0002104A1
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Prior art keywords
group
liquid crystal
dye
formula
anthraquinone
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Granted
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EP78300487A
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English (en)
French (fr)
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EP0002104B1 (de
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Jennifer Constant
Martin Geoffrey Pellatt
Iain Hugh Cunningham Roe
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BDH Chemicals Ltd
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BDH Chemicals Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
    • C09B1/50—Amino-hydroxy-anthraquinones; Ethers and esters thereof
    • C09B1/51—N-substituted amino-hydroxy anthraquinone
    • C09B1/514—N-aryl derivatives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
    • C09B1/16—Amino-anthraquinones
    • C09B1/20—Preparation from starting materials already containing the anthracene nucleus
    • C09B1/206—Dyes with amino groups substituted by heterocyclic radicals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
    • C09B1/16—Amino-anthraquinones
    • C09B1/20—Preparation from starting materials already containing the anthracene nucleus
    • C09B1/26—Dyes with amino groups substituted by hydrocarbon radicals
    • C09B1/32—Dyes with amino groups substituted by hydrocarbon radicals substituted by aryl groups
    • C09B1/325—Dyes with no other substituents than the amino groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
    • C09B29/0074—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing nitrogen and sulfur as heteroatoms
    • C09B29/0077—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing nitrogen and sulfur as heteroatoms containing a five-membered heterocyclic ring with one nitrogen and one sulfur as heteroatoms
    • C09B29/0085—Thiazoles or condensed thiazoles
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
    • C09B29/08—Amino benzenes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
    • C09B29/08—Amino benzenes
    • C09B29/0805—Amino benzenes free of acid groups
    • C09B29/0807—Amino benzenes free of acid groups characterised by the amino group
    • C09B29/0809—Amino benzenes free of acid groups characterised by the amino group substituted amino group
    • C09B29/081—Amino benzenes free of acid groups characterised by the amino group substituted amino group unsubstituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino, aralkylamino or arylamino
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
    • C09B31/02—Disazo dyes
    • C09B31/04—Disazo dyes from a coupling component "C" containing a directive amino group
    • C09B31/043—Amino-benzenes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
    • C09B35/35—Trisazo dyes in which the tetrazo component is a diamino-azo-aryl compound
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B56/00—Azo dyes containing other chromophoric systems
    • C09B56/12—Anthraquinone-azo dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/60—Pleochroic dyes
    • C09K19/603—Anthroquinonic

Definitions

  • the present invention is concerned with pleochroic dyes suitable for use in solution with liquid crystal materials for electro-optic device applications.
  • Electro-optic display devices of certain known types depend upon liquid crystal properties displayed by certain compounds known as liquid crystal compounds or materials which display phases intermediate between the fully ordered crystalline state and the fully disordered liquid state, apart from certain temporary short range ordering that is present in most liquid phases.
  • liquid crystal phase there are two principal types of liquid crystal phase, the smectic mesophase in which the molecular ordering is of a substantially lamellar type and the nematic mesophase in which the ordering is substantially linear. Included sometimes as a sub-claim of the nematic mesophase and sometimes classified as a separate mesophase is the cholesteric mesophase. This last type has a helical order, arising from the presence of a chiral or optically active centre in the molecular composition of the material and this helical order is superimposed upon the linear order of the nematic mesophase.
  • Liquid crystal materials have the property of imposing their own ordering upon other molecules incorporated in the materials and having an appropriate molecular configuration or shape. This property is the basis of guest-host devices in which a "host" liquid crystal material has its orientation controlled by the application of electrical or magnetio fields and in turn imposes its order upon "guest" molecules of, for example,pleochroic dyes. These are dyes whose absorption properties vary with the orientation direction of the electric vector of light incident upon them relative to their own molecular alignment.
  • a suitable pleochroio dye has an elongated rod-like molecule which absorbs relatively little light passing along its longitudinal axis but has a maximum absorption of light having its electric vector oriented along the longitudinal axis of the molecule.
  • Such dye molecules when placed in a liquid crystal material can adopt an orientation which follows the molecular orientation given to the crystal material and taking advantage of this two broad classes of guest-host devices are possible based respectively upon a nematic (or Freedericksz effect) device and secondly upon a cholesteric to nematic phase-change device.
  • the liquid crystal material is originally oriented by known treatment of the inner surfaces of the container, eg glass plates bearing device electrodes, containing the liquid crystal material. This orientation is changed by application of an electric field between the device electrodes.
  • the guest dye material also changes its orientation resulting in a change in absorption of light passing along the axis of the electrical field giving a switchable electro-optic display.
  • the liquid crystal material has positive dielectric anisotropy and is or includes an optically active compound which causes the material to exhibit a cholesteric mesophase having a long-pitch helical ordering of short range (the "focal conic" state).
  • the device scatters incident light because the ordering is only short range.
  • the device is switched on the electrical field applied across the material imposes a linear nematic order parallel to the electric field which results in orientation of any guest dye molecules also parallel to the electrical field and provides minimum absorption in that direction.
  • the device is less scattering and a switchable display is obtained between the "on” and “off” states.
  • the dye enhances the contrast between the two states.
  • the guest molecules adopt as closely as possible the time averaged orientation of the host, however ,this is achieved only to a limited degree because of random thermal fluctuations.
  • the degree to which the orientation varies from the ideal is measured by a quantity known as the order parameter S which is given by the following equation: where cos 2 ⁇ is a time averaged term and 0 is the instantaneous angular orientation of the molecules with respect to the time averaged orientation of the host molecules.
  • the determination of the value of the order parameter S is well understood in the art see for example the paper "A new absorptive mode reflective liquid crystal display device" by D L White and G N Taylor in the Journal of Applied Physics, 1974, 45 pages 4718 to 4723.
  • the order parameter S is one (that is 9 is zero) and pleochroic dyes for use in guest host devices should have an order parameter in the liquid crystal host as near one as possible but they must also have adequate chemical, photochemical and electrochemical stability, eg stability when exposed to atmospheric contaminants, electric fields (as in device operation) and to ultra-violet radiation. They should not be ionic or have any ionisable character and must also have sufficient solubility in the host materials although the concentrations of guest pleochroic dye required for the desired effect are generally quite small. The concentration is normally selected to ensure a light absorbance in the range of about 1.0 to 1.2 in the absorbing state of the cell, and of course depends upon cell thickness and the absorption coefficient of the dye. Typically this gives concentrations of pleochroic dye of up to about 1% by weight of the host material.
  • a liquid crystal material includes in solution therewith at least one pleochroic dye characterised in that the dye is an anthraquinone of general formula: Where R 2 is either hydrogen or a hydroxyl group, where R is an anilino or 3 or substituted or modified anilino group and where R is hydrogen when R 2 is a hydroxyl group and R 1 is an anilino or substituted or modified group group when R 2 is hydrogen.
  • R 4 may be any of the following groups: hydroxyl, alkyl, cycloalkyl, aryl hydroxyl, alkyloxy, alkoxyalkoxy, aryloxy, alkylamino, dialkylamino, alkyl or dialkylaminoalkoxy, nitrogen containing saturated heterocycles joined at the nitrogen atom, halogen (preferably chlorine), alkyloxy carbonyl, carboxyl alkyl or 4-oxybiphenylyl; If R 2 is hydrogen R 1 is preferably the same as R 2 .
  • Anthraquinone dyes of general formula (I) have been found to show reasonable order parameters, typically 0.5 or more (the precise figure depending in each on experimental conditions, eg the host material and device construction). In addition they have been found to show improved stability, particularly photochemical stability, compared with the dyes containing chains of azo-linked phenyl rings referred to above.
  • liquid crystal material and anthraquinone pleochroic dye are effectively in guest-host relationship and are thus suitable for use in electro-optic device applications.
  • the host liquid crystal material may be any liquid crystal compound or mixture of liquid crystal compounds but it has been found that mixtures of alkylcyanobiphenyls, alkyloxycyanobiphenyls and alkylcyanoterphenyls as disclosed and claimed in UK Patent Specifications No 1,433,130; 1,441,571 and 1,452,826 are particularly advantageous in the present invention.
  • R 4 may represent alkyl groups which are straight chain alkyl groups or branch chain alkyl groups which may include a chiral centre or R 4 may represent alkyloxy, alkoxyalkoxy, alkyl or dialkylamino, alkyl or dialkylaminoalkoxy, or dialkyloxycarbonyl groups similarly characterised.
  • the properties and usefulness of a guest material are determined principally by the shape and configuration that it adopts and in particular by the shape and configuration adopted by the group R 4 of Formula (II) above and so long as the guest achieves a "guest-host relationship" with the host material the identity of the group R 4 , so long as it falls within the classes delineated, is not critical.
  • an electro-optic device of the nematic (Freedericksz effect) or cholesteric-to-nematic phase change type includes a liquid crystal material including in solution therewith a pleochroic dye of general formula (I) above.
  • an electro-optic display cell 10 is shown in cross-section and consists of two glass plates 11 and 12 separated by a spacer 13. Each of the glass plates 11 and 12 has on its inner surface a transparent electrode 14 and 15 respectively, connected to a voltage source 16 through a switch 17 connected in series.
  • the space 18 within the electro-optic display cell 10 is filled with a guest-host liquid crystal material of the present invention.
  • the surfaces of the electrodes 14 and 15 may be treated by one of the methods well known to those skilled in the art to control the orientation of immediately adjacent liquid crystal molecules.
  • the voltage source 16 provides a voltage which is normally a low frequency alternating voltage as is well understood in the art.
  • the switch 17 When the switch 17 is open the applied voltage is zero and the liquid crystal molecules take up an appropriate orientation.
  • the device If the device is to operate as a cholesteric to nematic phase change device the molecules are oriented in helices of cholesteric mesophase corresponding to the focal ionic texture or the planar (Grandjean) texture. In both of these instances a guest dye molecule takes up the orientation of the host liquid crystal material and the layer 18 appears strongly coloured with the colour of the guest dye molecules because a substantial proportion of the molecules are oriented perpendicular to the direction of the incidence of the light upon the cell.
  • the host liquid crystal material if of positive dielectric anisotropy, is oriented along the line of the applied field and orients the guest dye molecules in the same direction.
  • the cell then appears clear or weakly coloured because the dye molecules do not significantly absorb light incident in the direction of the electric field, that is along the long axis of the dye molecule.
  • the electrodes may be shaped in the form of letters or numbers or other symbols sought to be displayed or there may be a multiplicity of electrodes forming individual members of symbols.
  • the cell may includee a reflector eg a white or coloured diffuse reflector, or a mirror behind the cell so as to improve the visibility of the symbol etc.
  • pleochroic anthraquinone guest materials are readily prepared by methods that will be apparent to one skilled in the art of chemical synthesis and typical synthesis of specific examples are given in Examples 1 to 5 below. Temperatures are given throughout in 0 0.
  • the orude dye (8.0g) was dissolved in dichloromethane and chromatographed on a column of alumina (800g, Merck Type T basic, deactivated with 40 ml water). The fractions containing pure dye were concentrated and passed through a column of silica gel (200g).
  • the dye solution was concentrated to saturation, ethanol (1.0 L) was added, and approximately 500 ml solvent was removed by distillation. The solution was set aside at 0°.
  • the product was found to have a solubility of 2.2% by weight in E7 at 25°C, and an absorption coefficient of 1.24 x 10 4 at 586 nm in chloroform solution.
  • the crude dye (8.0g) was dissolved in dichloromethane (200 ml), filtered, and adsorbed onto a column of silica gel (750g BDH deactivated with 112.5 ml water in 1 L dichloromethane). The column was eluted with dichloromethane. The fractions containing pure dye were concentrated to 400 ml and passed through a column of alumina (20g BDH basic activity 1, deactivated with 15% w/w water).
  • the dye solution was evaporated to 500 ml, ethanol (1 L.) was added, and 500 ml solvent was removed by distillation. The solution was set aside at 0°C.
  • the product was found to have a solubility of 0.8% by weight in E7 at 25°C and an absorption coefficient of 1.10 x 10 4 at 6 1 2 nm in chloroform solution.
  • the crude dye (8.2g) was dissolved in dichloromethane and chromatographed on a column of alumina (800 g BDH activity II). Fractons containing the pure dye were concentrated to 800 ml, ethanol (1.1 L.) was added and a further 600 ml solvent was removed by distillation. The solution was set aside at 0°C.
  • the product was found to have a solubility of 1.7% by weight in E7 at 25°C and an absorption coefficient of 1.58 x 10 4 at 554 nm in chloroform solution.
  • the crude dye (8.0g) was dissolved in dichloromethane and chromatographed on a column of alumina (800 g, BDH activity II). Fractions containing pure dye were concentrated to 800 ml, ethanol (1.1 L) was added, and 600 ml solvent was distilled from the solution, which was then set aside at 0°.
  • the product was found to have a solubility of 0.4% by weight in E7 at 25°C and an absorption coefficient of 1.50 x 10 4 at 557 nm in chloroform solution.
  • the crude dye (8.0g) was dissolved in 50% petrols dichloromethane (300 ml) and chromatographed on a column of silica gel (750 g BDH, deactivated with 20% w/w water). Fractions containing pure dye were concentrated to 800 ml, ethanol (1.0 L) was added and a further 700 ml solvent was removed by distillation. The solution was set aside at 0°.
  • the product was found to have a solubility of 0.8% by weight in E7 at 25°C and an absorption coefficient of 8.5 x 10 3 at 546 nm in chloroform solution.
  • Anthraquinones were prepared by the methods described above, or by modifioations thereof and materials were produced having the properties set forth in Tables 1 to 5 below. It should be noted that certain of the materials are quoted in the Tables for purposes of comparison and illustrate the effect of certain molecular changes upon the properties of anthraquinones of the present invention.
  • Table 1 gives absorption maxima and order parameters of three dyes described in a paper "Pleochroic Dyes with High Order Parameters" read by J Constant, E P Raynes, I A Shanks, D Coates, G W Gray and D G McDonnell at the Sixth International Liquid Crystal Conference at Kent State University in August 1976 and published in an abbreviated form in Electronics Letters.
  • the resistivity of the contents of the cell was measured at intervals for a period of up to 1500 hours, the mean of three determinations being taken and plotted to yield the graph displayed in Figure 2.
  • Resistivity measurements taken during the first few hours of such tests are not always trustworthy because, it is believed, trace quantities of metal ions are plated on to the electrodes of the cell.
  • the cells were the same as employed in Example 6 (a) using E7 as the liquid crystal host material.
  • the cells were placed on a heat sink 20cm form the lamp and had an average temperature of 25°C during the test.
  • the resistivity was measured at time intervals up to a total time of 100 hours.

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  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Liquid Crystal (AREA)
EP19780300487 1977-10-14 1978-10-11 Pleochroitische Farbstoffe geeignet zur Verwendung in Lösung mit flüssigen kristallinen Materialien für elektro-optische Einrichtungen Expired EP0002104B1 (de)

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GB4281077 1977-10-14
GB4281077 1977-10-14

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EP0002104A1 true EP0002104A1 (de) 1979-05-30
EP0002104B1 EP0002104B1 (de) 1982-10-20

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EP (1) EP0002104B1 (de)
JP (1) JPS5471088A (de)
CA (1) CA1140330A (de)
DD (1) DD141321A5 (de)
DE (1) DE2862064D1 (de)
GB (1) GB2011940B (de)

Cited By (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2426724A1 (fr) * 1978-05-23 1979-12-21 Minnesota Mining & Mfg Composition a base de colorants anthraquinoniques pleochroiques et son application a des dispositifs electro-optiques d'affichage
FR2451393A1 (fr) * 1979-03-16 1980-10-10 Mitsui Toatsu Chemicals Composition destinee a des elements d'affichage en couleur a cristaux liquides
US4232950A (en) * 1979-02-23 1980-11-11 Minnesota Mining And Manufacturing Company Liquid crystal compositions including pleochroic dye
US4232949A (en) * 1979-02-23 1980-11-11 Minnesota Mining And Manufacturing Company Liquid crystal compositions containing pleochroic dye
WO1981000463A1 (en) * 1979-07-27 1981-02-19 Minnesota Mining & Mfg Display device with dynamic internal polarizer
EP0025809A1 (de) * 1979-09-21 1981-04-01 BBC Aktiengesellschaft Brown, Boveri & Cie. Flüssigkristallmischung
US4279152A (en) * 1978-03-02 1981-07-21 International Standard Electric Corporation Temperature responsive device
US4288147A (en) * 1978-12-20 1981-09-08 Timex Corporation Electro-optical composition of the guest-host type
US4291948A (en) * 1977-11-10 1981-09-29 International Standard Electric Corporation Liquid crystal display incorporating positive and negative smectic material
US4299720A (en) * 1978-12-21 1981-11-10 Bbc Brown, Boveri & Co., Ltd. Liquid crystal mixture
US4304683A (en) * 1979-03-16 1981-12-08 Mitsui Toatsu Chemicals, Inc. Composition for liquid crystal color display element
WO1982000472A1 (en) * 1980-07-31 1982-02-18 V Nefedov Derivatives of 2,2-azoimidazole,method for the preparation thereof,liquid crystal material and electro-optical device
EP0054217A1 (de) * 1980-12-12 1982-06-23 Bayer Ag Anthrachinonfarbstoffe, Verfahren zu ihrer Herstellung, ihre Verwendung sowie flüssigkristalline Materialien enthaltend Anthrachinonfarbstoffe
EP0055989A3 (de) * 1980-02-26 1982-09-08 Siemens Aktiengesellschaft Flüssigkristall mit einem eingelagerten pleochroitischen Anthrachinon-Farbstoff und Verfahren zur Herstellung des Farbstoffes
US4356102A (en) * 1980-10-22 1982-10-26 General Electric Company Dichroic liquid crystal compositions containing anthraquinone-based dyes
DE3145711A1 (de) * 1981-11-19 1983-05-26 Basf Ag, 6700 Ludwigshafen Unloesliche verbindungen als farbgeber fuer fluessigkristallmischungen
US4389329A (en) * 1979-02-05 1983-06-21 Hoffmann-La Roche Inc. Meterocyclic compounds
US4391489A (en) * 1980-07-29 1983-07-05 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Liquid crystal materials containing pleochroic anthraquinone dyes
US4394070A (en) * 1980-07-16 1983-07-19 Minnesota Mining And Manufacturing Company Helichromic compounds and displays
US4405211A (en) * 1980-07-29 1983-09-20 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Liquid crystal compositions with pleochroic anthraquinone dyes
US4408840A (en) * 1980-09-22 1983-10-11 Hitachi, Ltd. Liquid crystal compositions containing pleochroic anthraquinone dyes, liquid crystal devices containing the compositions, and the dyes
US4446047A (en) * 1981-02-25 1984-05-01 Imperial Chemical Industries Plc Pleochroic anthraquinone dyes
FR2535733A1 (fr) * 1982-10-28 1984-05-11 Ivaschenko Alexandr V Derives de l'anthraquinone, leur procede de preparation, matiere a base de cristaux liquides les contenant et dispositif electro-optique utilisant celle-ci
US4455253A (en) * 1981-02-25 1984-06-19 Imperial Chemical Industries Plc Pleochroic anthraquinone dyes
US4456545A (en) * 1980-10-24 1984-06-26 Merck Patent Gesellschaft Mit Beschrankter Haftung Dichroitic anthraquinone dyestuffs useful in liquid crystalline dielectrics and electro-optical indicator elements
US4464282A (en) * 1981-02-25 1984-08-07 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britian And Northern Ireland Organic materials
US4466899A (en) * 1981-01-10 1984-08-21 Basf Aktiengesellschaft Dyes for use in liquid crystal mixtures
US4472292A (en) * 1981-07-02 1984-09-18 Merck Patent Gesellschaft Mit Beschrankter Haftung Liquid crystalline dielectric, new dichroitic naphthoquinone dyestuffs and electro-optical indicator element
US4495083A (en) * 1979-10-12 1985-01-22 Hitachi, Ltd. Guest-host type liquid crystal composition and liquid crystal display device using the same
US4496221A (en) * 1981-02-25 1985-01-29 Secretary of State for Defence in Her Britanic Majesty's Government of the United Kingdom of Great Britain and Northern Ireland of Whitehall Liquid crystal compositions with pleochroic anthraquines dyes
US4514045A (en) * 1981-06-22 1985-04-30 Minnesota Mining And Manufacturing Company Helichromic-smectic liquid crystal compositions and display cells
US4530572A (en) * 1982-12-30 1985-07-23 Minnesota Mining And Manufacturing Company Substituted anthraquinone-type isotropic dyes for liquid crystal display devices
EP0098522A3 (en) * 1982-06-30 1986-03-19 Hitachi, Ltd. Liquid crystal composition
US4624532A (en) * 1980-10-22 1986-11-25 General Electric Company Dichroic liquid crystal compositions containing anthraquinone-based dyes
US4702561A (en) * 1977-04-11 1987-10-27 Minnesota Mining And Manufacturing Company Pleochroic dyes and electro-optical displays therewith
US5026505A (en) * 1981-10-02 1991-06-25 Hitachi, Ltd. Guest-host type liquid crystal composition
CN108034275A (zh) * 2017-12-04 2018-05-15 蓬莱嘉信染料化工股份有限公司 一种蓝色分散染料和制备方法及其分散灰组合物

Families Citing this family (10)

* Cited by examiner, † Cited by third party
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JPS56100885A (en) * 1980-01-17 1981-08-13 Mitsui Toatsu Chem Inc Composition for liquid crystal color display
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US4702561A (en) * 1977-04-11 1987-10-27 Minnesota Mining And Manufacturing Company Pleochroic dyes and electro-optical displays therewith
US4291948A (en) * 1977-11-10 1981-09-29 International Standard Electric Corporation Liquid crystal display incorporating positive and negative smectic material
US4279152A (en) * 1978-03-02 1981-07-21 International Standard Electric Corporation Temperature responsive device
FR2426724A1 (fr) * 1978-05-23 1979-12-21 Minnesota Mining & Mfg Composition a base de colorants anthraquinoniques pleochroiques et son application a des dispositifs electro-optiques d'affichage
US4288147A (en) * 1978-12-20 1981-09-08 Timex Corporation Electro-optical composition of the guest-host type
US4299720A (en) * 1978-12-21 1981-11-10 Bbc Brown, Boveri & Co., Ltd. Liquid crystal mixture
US4389329A (en) * 1979-02-05 1983-06-21 Hoffmann-La Roche Inc. Meterocyclic compounds
US4232950A (en) * 1979-02-23 1980-11-11 Minnesota Mining And Manufacturing Company Liquid crystal compositions including pleochroic dye
US4232949A (en) * 1979-02-23 1980-11-11 Minnesota Mining And Manufacturing Company Liquid crystal compositions containing pleochroic dye
US4473486A (en) * 1979-03-16 1984-09-25 Mitsui Toatsu Chemicals, Inc. Composition for liquid crystal color display elements
FR2451393A1 (fr) * 1979-03-16 1980-10-10 Mitsui Toatsu Chemicals Composition destinee a des elements d'affichage en couleur a cristaux liquides
US4304683A (en) * 1979-03-16 1981-12-08 Mitsui Toatsu Chemicals, Inc. Composition for liquid crystal color display element
US4360447A (en) * 1979-03-16 1982-11-23 Mitsui Toatsu Chemicals, Inc. Composition for liquid crystal color display elements
WO1981000463A1 (en) * 1979-07-27 1981-02-19 Minnesota Mining & Mfg Display device with dynamic internal polarizer
EP0025809A1 (de) * 1979-09-21 1981-04-01 BBC Aktiengesellschaft Brown, Boveri & Cie. Flüssigkristallmischung
EP0026004A1 (de) * 1979-09-21 1981-04-01 BBC Aktiengesellschaft Brown, Boveri & Cie. Flüssigkristallmischung
US4495083A (en) * 1979-10-12 1985-01-22 Hitachi, Ltd. Guest-host type liquid crystal composition and liquid crystal display device using the same
EP0055989A3 (de) * 1980-02-26 1982-09-08 Siemens Aktiengesellschaft Flüssigkristall mit einem eingelagerten pleochroitischen Anthrachinon-Farbstoff und Verfahren zur Herstellung des Farbstoffes
US4363743A (en) * 1980-02-26 1982-12-14 Siemens Aktiengesellschaft Liquid crystals having pleochroic dyes
US4402854A (en) * 1980-02-26 1983-09-06 Siemens Aktiengesellschaft Liquid crystals having pleochroic dyes
EP0034832B1 (de) * 1980-02-26 1983-09-21 Siemens Aktiengesellschaft Flüssigkristall mit einem eingelagerten pleochroitischen Anthrachinon-Farbstoff und seine Verwendung
US4394070A (en) * 1980-07-16 1983-07-19 Minnesota Mining And Manufacturing Company Helichromic compounds and displays
US4483594A (en) * 1980-07-29 1984-11-20 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Liquid crystal materials containing pleochroic anthraquinone dyes
US4391489A (en) * 1980-07-29 1983-07-05 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Liquid crystal materials containing pleochroic anthraquinone dyes
US4405211A (en) * 1980-07-29 1983-09-20 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Liquid crystal compositions with pleochroic anthraquinone dyes
WO1982000472A1 (en) * 1980-07-31 1982-02-18 V Nefedov Derivatives of 2,2-azoimidazole,method for the preparation thereof,liquid crystal material and electro-optical device
US4408840A (en) * 1980-09-22 1983-10-11 Hitachi, Ltd. Liquid crystal compositions containing pleochroic anthraquinone dyes, liquid crystal devices containing the compositions, and the dyes
US4624532A (en) * 1980-10-22 1986-11-25 General Electric Company Dichroic liquid crystal compositions containing anthraquinone-based dyes
US4356102A (en) * 1980-10-22 1982-10-26 General Electric Company Dichroic liquid crystal compositions containing anthraquinone-based dyes
US4456545A (en) * 1980-10-24 1984-06-26 Merck Patent Gesellschaft Mit Beschrankter Haftung Dichroitic anthraquinone dyestuffs useful in liquid crystalline dielectrics and electro-optical indicator elements
US4585574A (en) * 1980-12-12 1986-04-29 Bayer Aktiengesellschaft Anthraquinone dyestuffs, processes for their preparation, their use, and liquid-crystalline materials containing anthraquinone dyestuffs
EP0054217A1 (de) * 1980-12-12 1982-06-23 Bayer Ag Anthrachinonfarbstoffe, Verfahren zu ihrer Herstellung, ihre Verwendung sowie flüssigkristalline Materialien enthaltend Anthrachinonfarbstoffe
US4466899A (en) * 1981-01-10 1984-08-21 Basf Aktiengesellschaft Dyes for use in liquid crystal mixtures
US4455253A (en) * 1981-02-25 1984-06-19 Imperial Chemical Industries Plc Pleochroic anthraquinone dyes
US4446047A (en) * 1981-02-25 1984-05-01 Imperial Chemical Industries Plc Pleochroic anthraquinone dyes
US4464282A (en) * 1981-02-25 1984-08-07 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britian And Northern Ireland Organic materials
US4496221A (en) * 1981-02-25 1985-01-29 Secretary of State for Defence in Her Britanic Majesty's Government of the United Kingdom of Great Britain and Northern Ireland of Whitehall Liquid crystal compositions with pleochroic anthraquines dyes
US4514045A (en) * 1981-06-22 1985-04-30 Minnesota Mining And Manufacturing Company Helichromic-smectic liquid crystal compositions and display cells
US4472292A (en) * 1981-07-02 1984-09-18 Merck Patent Gesellschaft Mit Beschrankter Haftung Liquid crystalline dielectric, new dichroitic naphthoquinone dyestuffs and electro-optical indicator element
US5026505A (en) * 1981-10-02 1991-06-25 Hitachi, Ltd. Guest-host type liquid crystal composition
DE3145711A1 (de) * 1981-11-19 1983-05-26 Basf Ag, 6700 Ludwigshafen Unloesliche verbindungen als farbgeber fuer fluessigkristallmischungen
US4588517A (en) * 1982-06-30 1986-05-13 Hitachi, Ltd. Liquid crystal composition
EP0098522A3 (en) * 1982-06-30 1986-03-19 Hitachi, Ltd. Liquid crystal composition
FR2535733A1 (fr) * 1982-10-28 1984-05-11 Ivaschenko Alexandr V Derives de l'anthraquinone, leur procede de preparation, matiere a base de cristaux liquides les contenant et dispositif electro-optique utilisant celle-ci
US4530572A (en) * 1982-12-30 1985-07-23 Minnesota Mining And Manufacturing Company Substituted anthraquinone-type isotropic dyes for liquid crystal display devices
CN108034275A (zh) * 2017-12-04 2018-05-15 蓬莱嘉信染料化工股份有限公司 一种蓝色分散染料和制备方法及其分散灰组合物
CN108034275B (zh) * 2017-12-04 2019-01-11 蓬莱嘉信染料化工股份有限公司 一种蓝色分散染料和制备方法及其分散灰组合物

Also Published As

Publication number Publication date
JPS6247230B2 (de) 1987-10-07
GB2011940A (en) 1979-07-18
CA1140330A (en) 1983-02-01
DE2862064D1 (en) 1982-11-25
JPS5471088A (en) 1979-06-07
DD141321A5 (de) 1980-04-23
EP0002104B1 (de) 1982-10-20
GB2011940B (en) 1982-10-27

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